Textile materials



A cicusly held gard to the The process may also be used for patterns oncloth-or sheets. thatthe afllnity of textile fibers,

cellulosic fibers truly become more wool-like in bothdyeing propertiesand physical properties."

,Patented Aug. 8, 1944 OFFICE TEXTILE MATERIALS Louis H. Bock,Hnntingdon Valley, and Alva L.

Honk, Philadelphia,

Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing.Application April Serial No. 381,682-

12 Claims.

This invention relates to theimprovement of textile materials bytreating them with condensates of formaldehyde and amides of malonicacid having at least one N-aminoalkyl substituent, thehydrocarboninterrupted by -NH- to form alkylene chains of at least twocarbon atoms. each between niportion of which may be es of improvingtextile trogen atoms. In the preferred form this in e ntion deals withaltering the, susceptibility of textile fibers to dyes by treatingfibers with said'con- Resins have heretofore been used in finishingtextile fabrics to impart increasedresilienceor stiffness, or to improvethe wearingjqualities of dyed fabrics by protecting the dye withadeposit of resin. Prior methods OtTQSm flnishinghave not, however,markedlychangedthe-afilnity be- 15 tion leads to tween fiber and dye.Nor have such methods permitted the with the same dyeing of differenttypesqof fiber dye or the eflective dyeing of cel-.

lulose with acid dyes; .In this last respect. at-V i tempts have beenmade to increase the afllnity of'cellulose for acid dyes bychemicaltreatments' reacting a mixture of formaldehyde and an aminoalkylmalonamide having a reactive methylene group in juxtaposition to theamide car bonyl group in the presence orjabsence of a solvent while thetemperature of the reacting mixture is held below about 100 C. Theaminoalkyl amides are obtained by reaction between a malonic ester andan alkylene polyamine, such as bis(aminopropyl) ethylene diamine,tripropylene tetramine, tris(trimethylene)tetramine, etc. or mixtures ofmonoand di-amides which are soluble in aqueous systems.

ethyl malonamide, N,N'-bis(aminoethyl)malonamide,.N,N'-bis(aminoethylaminoethyl)malonamide.N-aminoethylaminoethylaminoethyl propyl malonamlde. N,N'-bis(aminoethylaminoethylannnoethylaminoethyl) malonamide: etc. These amidesreact with aqueous or solvent solutions of which, while' oftenattackingcellulose fibers seformaldehyde or with formaldehyde from asolid verely, have not been particularly effective. I In 35 polymer toyield condensates which resinii'y on general such methods have beentoocomplicated further heating! To prevent prematuregelation anduneconomical to gain acceptance.

It ha been found that valuable improvements product of formforth. Thetreating is accomplished or impregnating the textile material with thesaid reaction product or with a solution thereof in water or organicsolvent. The treated material is heated at a temperature general- Itabove about 100 C. but below the decomposition temperature of thematerial being treated.

Textile materials so processed have an increased ailinity for acid dyesand acquire full,

deep shades when treated therewith. Other dyes ordinarily effective onlyon wool or silk are tenaby thus treated fibers without reoriginal typeof fiber. On the other hand, this treatment of textile materials'orfibers renders them resistant to various basic dyes. local efiects andyarns, or tabrics is'altered toward dyes, increased resilience isimparted withoutidevelopment Of a harsh or unpleasant handle 'ofethetextile material so that Thecondensates which areuseful in the procbytreating and:

as ethylene diamine,

of these condensates it is often desirable to condense the aminoamideand-formaldehyde in the presence'of a primary or secondary amine suchmethylamine, dimethylamine, diethylamine. cap 'ylmethylamine, etc.Details of the preparation and nature of the aminoamides andtheircondensates are given in applications having Serial N08. 387,679,387,680,

387,681 (now Patent No. 2,325,567). filed on even C. Temperatures of 120At the same time date. l

The formaldehyde-aminomalonamide con densates are applied to textilematerials from neutral, acidic, or alkaline solutions by spraying,dipping, padding,,..printing, or other method of treatment. Excesssolution is then desirably removed by a suitable means, such as acentrifugal extractor, vacuumslot extractor, or squeeze roll. Theimpregnated material is dried at room or higher temperature as aseparate step or as part of the baking step. It'is then baked above upto C. for 5 to 30 minutes are particularly effective in fixing thecondensate in the fibers, although temperatures as high as -160 C. maybe used in some cases. lfdesired, after this curing step the materialsmay be washed or secured in a bath of a natural or synthetic soap orother detergent. The materials may nowbe dyed with wool andsilk dyes llwith highly satisfactory results. The process-is fibers are obtainableby.

ethylene diamine, dlethylene triamine, triethylene, tetramine,tetraethylene pentamine, N,N'-,

polyal'kylene polyamines. This reac- Typical of the amino- T amideswhich result are N-aminoethylaminoethyl applicable to all types oftextile materials, including cotton, linen, regenerated cellulosefibers,

paper, straw, silk, fibers-or superlinear polymers,

Example 1 Ten parts of the reaction product obtained by heating togetherone mol of N,N-bis(aminoethylaminoethyl)malonamide, three mols offormaldehyde, and 3.5 mols of dimethylamine was taken up in water.Hydrochloric acid was added thereto until a pH of 6.8 was attained. Thesolution was then diluted with water to 100 parts. Bundles of rayonfiber (3 denier, 19/16" staple) were immersed in'the solution, whichwas-kept at the boil for five minutes. The bundles were removed from thetreating solution and squeezed to remove excess liquor. They were thendried and heated for 30 minutes in an oven at 125 C. The fibers showed adefinite increase in stiffness and were light tan in. color. The bundlesof fibers were accordingly washed in warm soap solution, which removedmost of the tan color. They were then placed for one-half hour in asimmering solution containing 1% Pontacyl Carmine 63 (Color Index No.57) and 41% of acetic acid. The 11-- bers were dyed a deep purple colorwhich was fast to washing and reasonably fast to light.

Example 2 Its greatest advantage is ob- Rayon taffeta was soaked forfive minutes in this solution while it was maintained at '70 C. andstirred from time to time.

The taifeta was run through squeeze rolls to remove excess solution anddried. It was then baked for one-half hour in an oven at 130 C. andwashed in a soap solution. The fabric was dyed in abath of Acid Brown EW#3 (Color Index No. 234) to a medium brown shade, which was fast.

Example 3 A 10% solution'of the reaction product of one mol ofN,N-bis(aminoethylaminoethylaminoethyl) malonamide and 1.5 mols offormaldehyde was madeslightly acid with hydrochloric acid. The solutionwas then used for the im- Example 4 Cotton cloth waslsoaked at 70 C. forfive minutes in a 20% solution of the reaction prod- 'uct from. one molof N,N'-bis(aminoethyl) malonamide, two mols of ethylene diamine, andone mol of formaldehyde. The cloth was removed from the solution andimmediately placed in an oven at 130 C. for a 40 minute period- Itpurple shade was then washed in soap solution anddyed in a bath ofPontacyl Carmine 63 to give a medium and two mols of formaldehyde-.- Thefabric was;- :7 dried, heated in an oven' at- C:-for.one-half; hour, andwashed in soap solution; It was'dyed in a bath of Brilliant W001 Blue(Prototype 40) The fabric was deep blueand retained this color. It wasnoticeably fuller and more resilient than untreated fabric and did notchange dimensions: appreciably on being laundered. e

Example 6 A 10% aqueous solution of the reaction product, obtained byheating at 70-80". C. amixture of 27.4 parts ofN,N'-bis(aminoethylamino-- ethyl)malonamide, 60 parts of dimethylamine,and 30 parts of 30% formaldehyde solution, was heated to 50 C. A hank ofnylon yarn was immersed in this solution for fifteen minutes andsqueezed free of excess solution. It was then dried and heated for 20minutes in an oven at C. The yarn was dyed in a bath of Pontacyl Carmine63. It retained a bright red color. Untreated nylon retained only a palecolor.

Example 7 The solution used in Example 6 was similarly applied to silkyarn, which was likewise dyed with Pontacyl Carmine 6B. A full red colorwas obtained. Yarn dyed directly without process-.

fabrics and stabilize fabrics against changes in dimensions. Theseimprovements appear due partly'to resinous deposits and partly to actualcombination between fiber and condensate or resin. Theformaldehyde-aminoalkyl malonamides may be applied to fibers as the solefinishing agent or they may be applied in conjunction with otherresin-forming materials such as ureaformaldehyde, acrylic resins, etc.or in conjunction with finishing agents such as sulfonated oils,long-chained quaternary ammonium salts, etc.

We claim:

1. The process of improving textile materials which comprises treatingsaid materials with the reaction product of formaldehyde and amalonamide having at least one N-aminoalkyl substituent, the hydrocarbonportion of which may be interrupted by --NH-- to form alkylene chains ofat least two carbon atoms each between nitrogen atoms, and heating thetreated materials above about 100 C. but below the decompositiontemperature of said materials.

2., The process of improving the affinity of cellulosic textile fibersto acid dyes which comprises impregnating said fibers with an aqueoussolution containing the reaction product of formaldehyde and amalonamide, having at least one N-polyamino polyalkylene substituent inwhich the alkylene chains consist of at least two carbon atoms each, andheating the impregnated fibers above about 100 C. but below thedecomposition temperature of said fibers.

3. The process of improving textile fibers, yarns, and fabrics whichcomprises impregnating said textile materials with a solution containingthe reaction product of formaldehyde and anN,N'-bis(polyaminopolyalkylene) malonamide, the alkylene chains of whichcontain at least two carbon atoms each, and heating the treatedmaterials above about 100 C. but below the decomposition temperature ofsaid materials.

4. The process of improving textile fibers, yarns, and fabrics whichcomprises impregnating said textile materials with a solution containingthe reaction product of formaldehyde and a malonamide, having at leastone N-aminoethylaminoethylaminoethylaminoethyl) group, and heating theimpregnated materials between about 100 C. and about 150 C.

5. The process of improving textile fibers, yarns, and fabrics whichcomprises impregnating said textile materials with a solution containingthe reaction product of formaldehyde andN,N'-bis(aminoethylaminoethylaminoethyl) malonamide, and heating theimpregnated materials between about'100 C. and about 150 C.

6. The process of improving textile fibers which comprises impregnatingsaid fibers with an aqueous solution of the reaction product offormaldehyde and N,N'--ibis(aminoethylaminoethyl)malonamide and heatingthe impregnated fibers between about 100" C. and about 150 C.

7. A textile material carrying the insolubilized reaction productofformaldehyde and a malonamide having at least' one N-amioalkylsubstituent, the hydrocarbon portion of which may be interrupted by --NHto form alkylene chains of at least two carbon atoms each betweennitrogen atoms.

8. A textile fabric carrying insolubilized thereon the reaction productof formaldehyde and an N,N-bis(polyaminopolyalkylene) malonamide,

the alkylene chains of which contain at least two carbon atoms each.

9. A textile material carrying insolubilized LOUIS H. BOCK. ALVA L.HOUK.

